Dyeing with sulphur black dyestuffs



Patented Mar. 12, 1949 PATENT ()FFICE DYEING WITH SULPHUR BLACK DYESTUFFS John L. ,Crist Charlotte, N. 0.,

assignor to Southern Dyestuffs Corporation, Charlotte,

NoDrawing. Application May 1 ,1939,

Serial No. 273,999

13 Claims. (01. 8-37) The present invention relates to the treatment of materials dyed with sulphur dyes and is concerned, in its broader aspect, with .the problem of preventing and/or inhibiting the tendency of ma? terials so dyed to tenderin storage and in sub-' sequent use. More particularly, the invention.

contemplates a treatment of cotton and other purely cellulosic fibres, dyed with sulphur black, whereby, as a result of said treatment, the dyed I) goods are rendered effectively resistant to tendering action and resultant reduction in tensile strength.

As is well known to those conversant with this art, sulphur black dyes, in and of themselves or 8 in combination with other sulphur dyes, have for many years been employed for the production of desirable fast black shades on various kinds and grades of textile materials, such as raw stock, yarns, threads and fabric. Comparative case of P application, consequent low cost of operation and inordinate fastness to light, milling and washing all contribute to the extremely large consumption of sulphur black dyes by the textile trade. The one limiting factor, however, in sulphur black use i is the recognized drawback that, under certain conditions of storage, such for example as storage in a warm, humid atmosphere, there is a marked tendency for the tensile strength of the dyed fibres, be they raw stock, yams, threads or woven textiles, to become materially reduced by socalled tendering action.- The presence of even minute quantities of iron or copper or other metals, or of salts thereof, greatly accelerates this tendering. Several theories have been advanced to explain tendering action, the most prevalent of which presupposes initial oxidation of the combined or active, low valent sulphur in the sulphur black, to sulphuric acid, and the subsequent attack of the cellulose structure by this acid. Un-

so controverted proof of this action has hardly been established, however, and consequently the'merits of the present invention are dependent in no way upon a satisfactory explanation of tendering action.

45 One object of my invention is to produce cotton and other cellulosic materials dyed with sulphur dyes, particularly sulphur black dyes, which are highly resistant to tendering in storage and other subsequent conditions. A further object is to 50 produce tendering resistant materials dyed either in the self shade, or when after-treated with, or contaminated by, metallic salts, such as salts of copper, iron, chromium, etc. A still further obiect is the provision of a new and improved proc- 1 ass for the production of materials of the ch'arac ter aforesaid. Other and further objects of my invention will become evident as the following description develops:

I have made the discovery that tendering of cotton goods dyed with sulphur dyes, and particu- 5 larly sulphur blackdyes, is effectively retarded or inhibited to a surprising degree by treating the goods in a solution of an amineof the char- 'acter set forthhereinafter. The amine solution is preferably dilute with respect to amine concen- 10 tration and may or may not contain added alkali or salt. In point of time, the after-treatment of the dyed goods with amine solutions may be carrled out at any convenient step in their manufacture, such for example as raw stock, roving,

yarn or piece goods. Alternately the amines may be incorporated with the starch and other finishing materials in the later finishing process of the goods.

Another alternative procedure, which may be considered as being encompassed within the broad scope of my invention, contemplates the introduction of amines having tendering inhibiting properties, directly into the preformed sulphur black dyestufi, when the latter is in either the reduced or oxidized state. 3

Amines coming within the scope of the present invention are those conforming to the following formula: Y''R(NI'IJ)1I wherein Y represents hydrogen or one or more hydroxyl groups or polyalkylene polyamine radicals, R is one or more hydrocarbon radicals, a: is a whole number from 0 to 2 inclusive to satisfy the valence of N, and n is a whole number. J

As illustrative of specific compounds falling 5 within the above category may be mentioned meta toluylene diamine having the formula para phenylenediamine and triethylene tetramine, having a polyalkylene polyamine radical,

HrN-CgHr-N-CrM-N-QHr-Nfla The amount of amine employed in the process of the invention may be varied within rather wide limits. For practical purposes about 1% (on phate. Goods so after-treated are, according to the weight of the dyed goods) appears to be sufflcient, although concentrations as'low as 0.1% and as high as 5%, or even higher, have been found to give beneficial results. These percentages are not to be taken as limitations since the amines maybe, and are intended to be, employed in any tendering inhibiting proportion.

As pointed out hereinbefore, when goods dyed with sulphur black come in contact with iron, or salts,thereof, tendering of the goods is greatly accelerated. Whether or not this is caused by the catalytic action of the iron (or its salts) in promoting the supposed oxidation of the sulphur in the sulphur black to destructive sulphuric acid, the fact remains that considerable trouble and expense is occasioned in-textile mills in attempting to prevent sulphur black dyed goods from coming into contact with iron, rusty iron or iron salts. In the practice of my invention, however, sulphur black dyed goods, which have been impregnated with an iron salt, such as ferric sulphate, become immune to tendering action to a remarkable and unexpected extent when treated with a dilute amine solution. 4

Another and very-important advantage flowing from the practice of my invention concerns the application thereof to sulphur black dyed goods which are after-treated with copper sul- Whittaker (Dyeing with Coal Tar Dyestufis, Industrial Chemistry Series, second ed., p. 102, 1926) so susceptible to tendering that this authority advises against any attempt whatsoever to use this chemical. Such is to be regretted, Whittaker states, since an after-treatment with copper sulphate beautifles the shade of many sulphur blacks. For the flrst.time, therefore, I have provided a process whereby sulphur black dyed goods may be after-treated with copper 1 sulphate without danger of subsequent tendering, heretofore considered impossible by worker in this art.

Aside from tendering inhibition, it has been found that the after-treatment with amines, in

- accordance with my invention, has an unexpected and beneficial effect upon the shade and depth tofore, goods of this character change their shade due to-natural processes of ageing and/or oxidation so that goods that are thoroughly aged are considerably redder in shade than when freshly dyed. This causes considerable trouble in matching shades because freshly dyed goods are always greener in tone than oxidized or aged goods. This shade change due to naturalageing can be induced by subjecting the dyeings to repeated heat treatments at approximately 140 C. with exposure to humid air between beatings.

When cotton goods are dyed with sulphur black k6 and'subjected to repeated heating at 140 0.,

the shade is veryperceptibly reddened and made somewhat weaker. This compares favorably with the shade change brought about under the natu-' found that when sulphur black dyed goods are after-treated with amines, in accordance with my preferred process,.the shade is not materially altered but the depth increases approximately to 20%.- If these goods are subjected to the above-described heat treatments there is practically no change in shade nor is there appreciable loss of depth. Untreated dyed goods, on the other hand, develop very much redder and lose approximately 10% of their depth.

I have made the further discovery that this after-treatment with amines on sulphur black dyed goods, without the use of oxidizing agents such as'sodium bichromate and acetic acid, produces not only fuller and deeper'shades but renders the dyed goods faster to washing and light. Recapitulating, where sulphur black dyeings are subjected to artificial ageing treatments, such as heating, or when aged naturally, the dyeings develop redder, lose a part of their depth and shade and also have their wash fastness impaired I whereas goods given a protective after-treatment with amines undergopractically no change of shade or depth nor do they lose their fastness properties.

It has been proposed heretofore to treat goods dyed with sulphur black, with amines and an oxidizing agent, the sole purpose of the treatment being to increase the intensity of shade and the fastness of the dyeing to light and milling. I have established by experimentation, however, that such a treatment not only does not inhibit or prevent tendering, but quite to the contrary, tendering in some cases is accelerated by this treatment.

As illustrative of the preferred procedure in carrying out my invention reference is had to the following specific examples which, it will be un derstood, are in no way limitative:

E :rample I Cotton yarn dyed with sulphur black made by the thionation of di and tri nitro phenol was, after dyeing, thoroughly washed. The yarn was then treated in a solution containing 5% (quantity computed on the weight of the yarn) of meta toluylene diamine at 85 C. for a period of 30 minutes, and then extracted and dried in the customary manner. The yarn thus treated and also a quantity of untreated yarn was then heated in.

an oven for four heats of 2 hours each at 140 0., being subjected to humid atmosphere for 20 hours between each heat. Both yarns were then tested as to tensile strength and the treated yarn was found to be 8 times as strong asthe untreated yarn.

Example II Cotton yarn dyed with sulphur black was thoroughly washed and then treated in a solution containing 5% meta toluylene diamine and -1% of soda ash (both computed on the weight'oi the yarn) at C. for a. period of approximately 30 minutes, after which it was extracted and dried in the customary manner. The thus treated yarn, and also a quantity of untreated dyed yarn, was then heated in an oven for four heats of 2 hours each at 140 0., being subjected to humid atmosphere for reconditioning between each heat. When tested for tensile strength it was found that the treated yarn was 8 times as strong as the untreated yarn.

Example III Cotton yarn dyed with sulphur black was thoroughly washed and then treated in a solution containing 5% meta toluylene diamine, 1% soda ash and 5% salt (all quantities'computed on the weight of the yarn) at 60 C. for approximately 30 minutes, after which it was extracted and dried in the customargisnner. The thus treated yarn, and also a q tity of untreated dyed yarn, was then heated in amen for tour heat! of 2 hours each at 140 0., being subjected'to v humid .atznospherefor reconditioning between .each heat. when tested for tensile strength it was found that the treated yarn was 8 times as strong as the untreated yarn. v}

Example IV Cotton yarn dyed with sulphur black dye was thoroughly washed and then treated in a solution containing 5% para phenylene diamine and 1% soda ash (quantities computed on the weight of the yarn) at 60 C. for a period of approximately minutes. The yarn was then extracted and dried in the customary. manner. 1 Upon being subjected to alternate heating and humidifying the yarn so treated was found to be 8,times as strong as untreated yarn.

Example Cotton yarn dyed with sulphur black dye was 7 thoroughly washed and then treated with a solution containing 5% triethylene tetramine, 1%

soda ash and 5% salt (all quantities computed on the weight of the yarn) at 65 C. for a period of approximately-30 minutes. Upon being subjected to alternate heating and humidifying the yarn so treated was found to be 7 times as strong as untreated yam. r

Ex'r -ple VI Cotton yarn dyed with sulphur black dye was thoroughly washed and then treated with a solution containing 5% triethanol amine, 1% soda ash, and 5% salt (all quantities computed on the I weight of the yarn) at 65 C. for a period of approximately 30 minutes. Upon being subjected to alternate heating and humidifying theyarn so treated was found to be 5 times as strong as untreated yarn.

' Example VII Cotton goods dyed with sulphur black dye were treated in a finishing process where 2% of meta toluylene diamine (on the. weight of the goods) was added to the finishing materials, after which the dyed goods were dried in'the customary man ner. Upon being subjected-to alternate heating and humidifying the goods so treated were found to be 6 times as strong as untreated goods subjected to regular. finishing materials.

Example VIII mtyam dyed withsulphur black dye was after-treated with acetic acid and copper sulphate for the purpose of improving the depth of shade and the'fastness' of the dyeing to light and washing. This dyed and after-treated yarn was then subjected to a further treatment in a solution containing 5% meta toluylene diamine and 1% soda'ash (quantity computed on the weight'of the yarn) at 60 C. for 30 minutes. The yarn treated with meta toluylene diamine and that given no protective treatment were-subv jected to heat and humidifying treatments as in previous examples, after which the yarn was tested for tensile strength. The yarn aftertreated with the protecting amine was found to be much more resistant'to tendering and 7 times as strong as the yarn given no protective treatment.

Example IX Cotton yarn dyed with sulphur black dye was purposely impregnated with ferric sulphate (5% on the weight of the ,yarn), after which it was given on protective treatment in a solution containingl2% meta toluylene diamine, 1% soda ash and 5% salt (quantity computed on the weight of the yarn) at C. for- 30 minutes. The yarn treated with the amine and a further quantity of yarn given no protective \treatment were subjected to heat and humidifying treatments as in previous examples, after which the yarns were tested for tensile strength. The yarn after-' treated with the protecting amine was found to be much more resistant to tendering and 20 times as strong as the yarn given no protective treatment.

Example X Cotton goods .dyed with sulphur black were cut into two portions. One portion was given no protective treatment while the second portion was given a protective treatment with a solution containing 2% of meta toluylene'diamine (quantities figured on the weight of the goods) as above described. Both of these portions were then subjected to heating at C. for 2 hours and then exposed in humid atmosphere for 20 hours. This treatment was repeated three times.

It was found that the shade of the untreated portion had developed many shades redder than a fresh dyeing unheated, whereas the shade or the tone of the portion that had been given the protective treatment had undergone practically no change and had essentially the same shade as a fresh unheated dyeing.

Example XI divided into two portions. On one portion no further treatment was given. On the second the protective treatment referred to above with a solution containing 2% of meta toluylene diamine (on the weight of the goods) was given. No oxidizing agent such as sodium bichromate and acetic acid was used. The intensity of shade of the portion given the protective treatment was 15% heavier and deeper than the depth of shade of the portion that received no treatment.

Example XII Cotton goods dyed with sulphur black made by the thionation of di and tri nitro phenol were, after dyeing, thoroughly washed. The goods were then treated in a solution containing 5% (quantity computed on the weight of the goods) of para aminophenol at 85C. for a period of 30 minutes, and then extracted and dried in the customary manner. The goods thus treated and also a quantity of untreated goods were then heated in an oven for four heats of 2 hours each at 140'C., being subjected to humid atmosphere for 20 hours between each heat. Both goods were then tested as to tensile strength and the treated goods were found to be 6 times as strong as the untreated goods.

Example XIII Cotton goods dyed with sulphur black were thatzthe treated goods were 4 times as strong as the untreated goods.

While the invention is not limited by any particulartheory it should be mentioned that tendering of the goods is apparently inherent in the sulphur dye rather" than in the material treated.

It will be understood that the tendering inhibitors herein described may, in accordance with the invention, be applied to any cellulosic material which is dyed with a sulphur dye. The efli'- ciency of the tendering inhibitors herein described is such that sulphur black dyed material, 'or other sulphur dyed materials, treated therewith remain substantially unaltered after long periods of storage even in warm damp places.

I claim:

1. Cellulosic goods dyed with sulphur black produced by thionating a nitro-phenol, said goods being susceptible to tendering'and having thereon, in an amount suflicient to inhibit tenderin of the dyed goods, an amineof the following formula: YR(NH,1:)11 wherein Y is at least one radical selected from the group consisting of hydrogen, hydroxyl and polyalkylene polyamine, R is at least one hydrocarbon radical, a: is zero or a whole number less than 3 to satisfy the valence of N, and n is a whole number.

2. A process for inhibiting tendering in cotton' goods and other cellulosic fibers dyed with sulphur blac which comprises treating said goods or fibers, the absence of an added oxidizing agent, with a solution containing an amine in an amount suilicient to inhibit tendering of the dyed goods, said amine having the following formula: Y-R-(NHeM wherein Y is at least one radical selected from the group consisting of hydrogen,

hydroxyl and polyalkylene polyamine, R is at least one hydrocarbonradical, a: is zero or a whole number lessthan 3 to satisfy the valence of N, and n is a whole number.

3. A process for inhibiting tendering in cotton goods and other cellulosic fibres dyed with sulphur black which comprises treating said goods or fibres, in. the absence of an added oxidizing agent, with a solution containing 0.1% .to 5.0%,

. on the weight of the goods, of an amine effective 6. Qotton goods cient to inhibit tendering of the dyed goods.

5. Cotton goods'dyed with sulphur black produced by thionating a nltro-phenol, said goods being susceptible totendering and having thereon para phenylene diamine in an amount sufllcient to inhibit tendering of the dyed goods.

e a nitro-phenol, said goods "ceptible to'itendering and having thereon trigtliylene tetramine in an amount sufllcient to inhibit tendering of the dyed goods.

7. Cellulosic goods dyed with sulphur black and containing an, iron compound, said goods being d 'with sulphur black prosusceptible to tendering and having thereon, in

an amount suiiicient to inhibit tendering of the.

dyed goods, an amine of the following formula: Y-R-(NHe); wherein Y is at least one radical selected from the group consisting of hydrogen, hydroxyl and polyalkylene polyamine, R is at least one hydrocarbon radical, a: is zero or a whole number less than 3 to satisfy the valence of N,

' selected from "the group consisting of hydrogen,

hydroxyl and polyalkylene polyamine, R is at least one hydrocarbon radical, a: is zero or a whole number less than 3 to satisfy the valence of N, and n is a whole number.

9. A process for inhibiting tendering in cotton goods and other cellulosic fibres dyed withsulphur black and containing an iron compddnd,

which comprises after-treating said goods or,

fibres, in the absence of an added oxidizing agent, with a solution containing an amine in an amount sufiicient to inhibit tendering of the dyed goods, said. amine having the following formula: Y--R(NH.-.-)fl wherein Y is at least one radical selected from the group consisting of hydrogen, hydroxyl and polyalkylene polyamine, R is ,at

least one hydrocarbon radical, a: is zero or a whole number less than 3 to satisfy the valence of N, and n is a whole number. I

10. A process for inhibiting tendering in cotton goods and other cellulosic fibres dyed with sulphur black and containing a copper compound, which comprises after-treating. said goods or fibres, in the absence of an added oxidizing agent,

least one hydrocarbon radical, a: is zero or a'whole number less than 3 to satisfy the valence of N, and n is a whole number.

11. A process for inhibiting tendering in cotton goods and other cellulosic fibres dyed with sulphur black which comprises after-treating said goods or fibres, in the absence of an added oxidizing agent, with a solution containing meta .tolu-ylene diamine in an amount sumcicnt to inhibit tendering of the dyed goods.

12. A process for inhibiting tendering in cotton goods and other oellulosid fibres dyed with sulpnur black which comprises after-treating said goods orfibres. in the absence 01' an added 03- dizing agent, with a solution containing para dizing agent, with a solution containing triethylene tetramine in an amount sufi'icient to inhibit tendering of the dyed goods.

. JNO. L. CRIST. 

